Tempered glass substrate and method of producing the same

ABSTRACT

A tempered glass substrate has a compression stress layer on a surface thereof, and has a glass composition comprising, in terms of mass %, 40 to 70% of SiO 2 , 12 to 21% of Al 2 O 3 , 0 to 3.5% of Li 2 O, 10 to 20% of Na 2 O, 0 to 15% of K 2 O, and 0 to 4.5% of TiO 2 , wherein the tempered glass substrate has a plate thickness of 1.5 mm or less, and an internal tensile stress in the tempered glass substrate is 15 to 150 MPa.

This application is a divisional application of U.S. application Ser. No. 12/320,786, filed Feb. 4, 2009, which is a continuation-in-part application of International Patent Application No. PCT/JP2008/062941, field Jul. 17, 2008, and claiming the priorities of Japanese application 2007-203604, filed Aug. 3, 2007 and 2008-154906, filed Jun. 13, 2008.

TECHNICAL FIELD

The present invention relates to a tempered glass substrate, and particularly, to a tempered glass substrate suitable for cellular phones, digital cameras, personal digital assistance (PDA), solar battery cover glass, or touch panel display substrates.

BACKGROUND ART

Devices such as cellular phones, digital cameras, PDA, solar batteries, or touch panel displays are widely used, and show a tendency of further prevalence.

Conventionally, for those applications, resin substrates made of acryl and the like are used as a protective member for protecting a display. However, the acrylic resin substrate easily bends, because of its low Young's modulus, when the screen of a display is pushed by a pen, human finger and the like, thus, the resin substrate comes into touch with an internal display to generate poor display, in some cases. There is also a problem in that flaw is easily formed on the surface of the acrylic resin substrate, and visibility tends to deteriorate. One method for solving those problems is to use a glass substrate as a protective member. The glass substrate (cover glass) to be used as the protective member is required (1) to have high mechanical strength, (2) to be low in density and light in weight, (3) to be cheap and to be supplied in a large amount, (4) to have excellent bubble quality, (5) to have high optical transmittance in the visible region, and (6) to have high Young's modulus to prevent bending in pushing the surface with a pen, finger, and the like. In particular, when the requirement (1) is not satisfied, a role as the protective member is not attained, thus, glass substrates tempered by ion exchange and the like (so-called tempered glass substrate) are conventionally used (see Patent Document 1, Non-patent Document 1).

-   Patent Document 1: JP 2006-83045 A -   Non-patent Document 1: Tetsuro Izumitani et al., “New glass and     physicality thereof”, First edition, Management System Laboratory.     Co., Ltd., Aug. 20, 1984, p 451-498

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

Non-patent document 1 describes that when the content of Al₂O₃ in the glass composition is increased, the ion exchange performance of the glass increases and the mechanical strength of the glass substrate can be improved.

However, when the content of Al₂O₃ in the glass composition is further increased, the devitrification resistance of the glass deteriorates, the glass tends to be devitrified in forming, and the production efficiency, quality, and the like of the glass substrate becomes worse. When the devitrification resistance of the glass is poor, forming is only possible by a method such as roll molding, and a glass plate having high surface precision cannot be obtained. Therefore, after forming of the glass plate, a polishing process should be additionally performed separately. When the glass substrate is polished, however, small defects tend to be generated on the surface of the glass substrate, and it becomes difficult to maintain the mechanical strength of the glass substrate.

In view of the above circumstances, it is difficult to attain the ion exchange performance and the devitrification resistance of a glass simultaneously, and it is difficult to remarkably improve the mechanical strength of the glass substrate. For reducing the weight of a device, glass substrates used in devices such as touch panel displays are reduced in thickness year by year. Because a glass substrate with small thickness is easily broken, technologies for improving the mechanical strength of the glass substrate are becoming more important.

Thus, it is a technical object of the present invention to obtain a glass substrate having high mechanical strength by satisfying the ion exchange performance and the denitrification resistance of a glass simultaneously.

Means for Solving the Problems

The inventors of the present invention have conducted various studies and resultantly found that, by setting an Al₂O₃ content and a Na₂O content in a glass in appropriate ranges, high ion exchange performance and meltability can be ensured. Also, it has been found that restriction of an internal tensile stress to a predetermined range enable to prevent the glass from breaking due to internal defects while securing a required mechanical strength, and thus, leading to the proposal of the present invention.

That is, the tempered glass substrate of the present invention has a compression stress layer on a surface thereof, and has a glass composition including, in terms of mass %, 40 to 70% of SiO₂, 12 to 21% of Al₂O₃, 0 to 3.5% of Li₂O, 10 to 20% of Na₂O, 0 to 15% of K₂O, and 0 to 4.5% of TiO₂, wherein the tempered glass substrate has a plate thickness of 1.5 mm or less, and wherein an internal tensile stress in the tempered glass substrate is 15 to 150 MPa. Note that, unless otherwise mentioned, “%” means “mass %” in the following descriptions.

The tempered glass substrate of the present invention is preferable to having a plate thickness of 0.7 mm or less. Internal tensile stress in glass substrate=(compression stress value×stress layer depth)/(plate thickness−stress layer depth×2)

The tempered glass substrate of the present invention is preferable to being chemically tempered.

In the tempered glass substrate of the present invention, a compression stress of the surface is preferably 300 MPa or more.

In the tempered glass substrate of the present invention, a depth of the compression stress layer is preferably 10 μm or more. Here, “compression stress of surface” and “depth of compression stress layer” are calculated from the number of interference stripes and clearance thereof obtained in observing a sample using a surface stress meter (FSM-6000 manufactured by Toshiba Corporation). The internal tensile stress in the glass substrate is calculated by the above formula.

The tempered glass substrate of the present invention is preferable to having an unpolished surface. Here, “unpolished surface” means that both surfaces (so-called front surface and rear surface) of a glass substrate are not polished. In other words, it means that both surfaces are fire polishing surfaces, and by this, it becomes possible to decrease the average surface roughness (Ra). The average surface roughness (Ra) is measured by a method according to SEMI D7-97 “Measurement method of surface roughness of FPD glass substrate”, and should be 10 Å or less, preferably 5 Å or less, and more preferably 2 Å or less. Note that an end surface of the glass substrate may be subjected to a polishing treatment or an etching treatment such as chamfering.

The tempered glass substrate of the present invention is preferable to having a liquidus temperature of 1200° C. or lower. Here, a glass is ground, and a glass powder passing through a standard sieve of 30 mesh (mesh opening 500 μm) and remaining on 50 mesh (mesh opening 300 μm) is placed in a platinum boat, kept in a temperature gradient furnace for 24 hours, then, the crystal thereof deposits, and the temperature at this stage is referred to as “liquidus temperature”.

The tempered glass substrate of the present invention is preferable to having a liquidus viscosity of 10^(4.0) dPa·s or more. Here, “liquidus viscosity” denote the viscosity of a glass at the liquidus temperature. When the liquidus viscosity is higher and the liquidus temperature is lower, the denitrification resistance of a glass is improved, and forming of a glass substrate becomes easy.

The tempered glass substrate of the present invention is preferably used as a cover glass of a display.

Further, the tempered glass substrate of the present invention is preferably used as a cover glass of a solar battery.

Further, a method of producing a tempered glass substrate of the present invention comprises the steps of melting a glass raw material which is prepared to have a glass composition including, in terms of mass %, 40 to 70% of SiO₂, 12 to 21% of Al₂O₃, 0 to 3.5% of Li₂O, 10 to 20% of Na₂O, 0 to 15% of K₂O, and 0 to 4.5% TiO₂, forming the resultant into a plate shape having a plate thickness of 1.5 mm or less, and performing an ion exchange treatment to form a compression stress layer on a surface of the glass and an internal tensile stress of 15 to 150 MPa in the glass.

Effect of the Invention

The tempered glass substrate of the present invention is manufactured by using glass showing high ion exchange performance. The tempered glass substrate is manufactured using a glass excellent in denitrification resistance, and hence, it is possible to obtain a glass substrate having small surface roughness by adopting an overflow down draw method or the like. Therefore, polishing after forming is unnecessary, and small defects occurred by polishing are not present. As a result, mechanical strength is high, and there is no increase in production cost by polishing, and inexpensive production is possible.

The tempered glass substrate of the present invention is suitable as a cover glass and a touch panel display substrate for cellular phones, digital cameras, PDA, and solar batteries. Note that a touch panel display is mounted on cellular phones, digital cameras, PDA, and the like, and a touch panel display for mobile application is required to attain weight reduction, thickness reduction, and tempering, therefore, there is required, a glass substrate of thin type having high mechanical strength. In this point, the tempered glass substrate of the present invention is suitable for mobile application, because if the plate thickness thereof is reduced, the substrate has practically sufficient mechanical strength.

The glass of the present invention can be formed by an overflow down draw method and the like, because the glass has excellent denitrification resistance. Therefore, when the glass of the present invention is used, a glass substrate having small surface roughness and high mechanical strength can be produced at low cost.

Because the method of producing a tempered glass of the present invention uses a glass having high ion exchange performance and excellent devitrification resistance, a tempered glass substrate having high mechanical strength can be manufactured at low cost.

DESCRIPTION OF EMBODIMENTS

The tempered glass substrate of the present invention has a compression stress layer on a surface thereof. The method of forming the compression stress layer on the surface of a glass substrate includes a physical tempering method and a chemical tempering method. For the tempered glass substrate of the present invention, a compression stress layer is formed preferably by a chemical tempering method. The chemical tempering method is a method of introducing alkali ions having large ion radius onto the surface of a glass substrate by ion exchange at a temperature lower than a strain point of the glass. When a compression stress layer is formed by the chemical tempering method, the tempering treatment can be performed successfully even if the plate thickness of the glass substrate is small, and desired mechanical strength can be obtained. Further, even if the glass substrate is cut after the formation of a compression stress layer on the glass substrate, it is not broken easily like a glass substrate tempered by a physical tempering method such as an air cooling tempering method.

The conditions for ion exchange are not particularly limited, and may be determined in view of the viscosity property and the like of a glass. In particular, it is preferred that a K ion in a KNO₃ molten salt be ion-exchanged for a Na component in a glass substrate, because a compression stress layer can be formed efficiently on the surface of the glass substrate.

The reason for limiting the glass composition to the above-mentioned range in the tempered glass substrate of the present invention is illustrated below.

SiO₂ is a component forming a network of a glass, and content thereof is 40 to 70%, preferably 40 to 63%, 45 to 63%, or 50 to 59%, and particularly preferably 55 to 58.5%. When the content of SiO₂ is too large, melting and forming of the glass become difficult, the thermal expansion coefficient becomes too small, and matching of the thermal expansion coefficient with those of peripheral materials becomes difficult. On the other hand, when the content of SiO₂ is too small, glass formation becomes difficult. Further, the thermal expansion coefficient of the glass becomes large, and the thermal shock resistance of the glass tends to lower.

Al₂O₃ is a component enhancing ion exchange performance. It has also an effect of enhancing the strain point and the Young's modulus of a glass, and the content thereof is 12 to 21%. When the content of Al₂O₃ is too large, a devitrified crystal tends to deposit in the glass and forming by an overflow down draw method and the like becomes difficult. Further, the thermal expansion coefficient of the glass becomes too small, and matching of the thermal expansion coefficient with those of peripheral materials becomes difficult, and the high temperature viscosity of the glass rises, and it becomes difficult to melt the glass. When the content of Al₂O₃ is too small, there occurs a possibility of no manifestation of a sufficient ion exchange performance. From the above-mentioned viewpoints, it is more preferred that the upper limit of the suitable range of Al₂O₃ be 20% or less, 19% or less, 18% or less, 17% or less, or 16.5% or less. It is more preferred that the lower limit thereof be 13% or more, or 14% or more.

Li₂O is an ion exchange component, and is also a component lowering the high temperature viscosity of a glass to improve the meltability and the formability thereof. Further, Li₂O is a component improving the Young's modulus of the glass. Further, Li₂O has a high effect of enhancing the compression stress value in an alkali metal oxide. However, when the content of Li₂O is too large, the liquidus viscosity lowers and the glass tends to be devitrified. Further, the thermal expansion coefficient of the glass increases too much, and hence, the thermal shock resistance of the glass lowers, and matching of the thermal expansion coefficient with those of peripheral materials becomes difficult. Further, when the low temperature viscosity is lowered too much to cause a possibility that stress relaxation occurs easily, the compression stress values decreases adversely in some cases. Therefore, the content of Li₂O is 0 to 3.5%, further, it is preferably 0 to 2%, 0 to 1%, 0 to 0.5%, or 0 to 0.1%, and substantially no content, namely, suppression to less than 0.01% is most preferable.

Na₂O is an ion exchange component, and is also a component lowering the high temperature viscosity of a glass to improve the meltability and the formability thereof. Further, Na₂O is also a component improving the denitrification resistance of the glass. The content of Na₂O is 10 to 20%, and more suitable content thereof is 10 to 19%, 12 to 19%, 12 to 17%, or 13 to 17%, and particularly 14 to 17%. When the content of Na₂O is too large, the thermal expansion coefficient of the glass becomes too large, and hence, the thermal shock resistance of the glass lowers, and matching of the thermal expansion coefficient with those of peripheral materials becomes difficult. Further, there are tendencies that the strain point lowers too much, and a balance of the glass composition is lacking, thereby deteriorating the devitrification resistance of the glass. On the other hand, when the content of Na₂O is small, meltability deteriorates, the thermal expansion coefficient becomes too small, and the ion exchange performance deteriorates.

K₂O has an effect of promoting ion exchange, and shows a high effect of enlarging the depth of a compression stress layer, among alkali metal oxides. Further, K₂O is a component having an effect of lowering high temperature viscosity to enhance the meltability and the formability. K₂O is also a component improving devitrification resistance. The content of K₂O is 0 to 15%. When the content of K₂O is too large, the thermal expansion coefficient of a glass becomes large, the thermal shock resistance of the glass lowers, and matching of the thermal expansion coefficient with those of peripheral materials becomes difficult. Further, there are tendencies that the strain point lowers to much, and a balance of the glass composition is lacking, thereby deteriorating the devitrification resistance of the glass, thus, it is preferred that the upper limit be 12% or less, 10% or less, 8% or less, 6% or less, 5% or less, 4% or less, 3% or less, or 2% or less.

When the total content of alkali metal oxides R₂O (R represents one kind or more selected from Li, Na, and K) is too large, the glass tends to be devitrified, and in addition, the thermal expansion coefficient of the glass becomes too large, and hence, the thermal shock resistance of a glass lowers, and matching of the thermal expansion coefficient with those of peripheral materials becomes difficult. Further, when the total content of the alkali metal oxides R₂O is too large, the strain point of the glass lowers too much, and a high compression stress value is not obtained in some cases. Further, the viscosity around the liquidus temperature lowers, and it becomes difficult to obtain high liquidus viscosity in some cases. Therefore, it is preferred that the total content of R₂O be 22% or less or 20% or less, and particularly 19% or less. On the other hand, when the total content of R₂O is too small, the ion exchange performance and the meltability of the glass deteriorate in some cases. Therefore, it is preferred that the total content of R₂O be 8% or more, 10% or more, or 13% or more, and particularly 15% or more.

It is desirable that the value of (Na₂O+K₂O)/Al₂O₃ is set in the range of 0.7 to 2, preferably 0.8 to 1.6, more preferably 0.9 to 1.6, still more preferably 1 to 1.6, and most preferably 1.2 to 1.6. When the value becomes more than 2, there are tendencies that the low temperature viscosity lowers too much and the ion exchange performance lowers, the Young's modulus lowers, and the thermal expansion coefficient becomes large, thereby lowering the thermal shock resistance. Further, a balance of the composition is lacking, and the glass tends to be devitrified. On the other hand, when the content is smaller than 0.7, the meltability and the denitrification resistance tend to deteriorate.

Further, the range of the mass ratio of K₂O/Na₂O is preferably 0 to 2. By changing the mass ratio of K₂O/Na₂O, the compression stress value and the depth of the stress layer can be changed. When it is desired to set the compression stress value high, it is preferred that the above-mentioned mass ratio be adjusted to be 0 to 0.5, and particularly 0 to 0.3, or 0 to 0.2. On the other hand, when it is desired to make the stress depth larger and to form deeper stress in a short period of time, it is preferred to adjust the above-mentioned mass ratio to 0.3 to 2, and particularly to 0.5 to 2, 1 to 2, 1.2 to 2, or 1.5 to 2. Here, the reason for setting the upper limit of the above-mentioned mass ratio to 2 is that if the mass ratio is more than 2, the glass composition lacks balance, and the glass tends to be devitrified.

In the tempered glass substrate of the present invention, the glass composition may be constituted only of the above-mentioned basic components. However, other components can also be added in a range not significantly deteriorating the property of the glass.

For example, alkaline earth metal oxides R′O (R′ represents one kind or more selected from Mg, Ca, Sr, and Ba) are components which can be added for various purposes. However, when the total content of the alkaline earth metal oxides R′O becomes large, the density and the thermal expansion coefficient of the glass becomes large, and the denitrification resistance deteriorates, and in addition, the ion exchange performance tends to deteriorate. Therefore, the total content of the alkaline earth metal oxides R′O should be preferably 0 to 9.9%, 0 to 8%, 0 to 6%, or 0 to 5%.

MgO is a component which lowers the high temperature viscosity of a glass to enhance the meltability and the formability, or to enhance the strain point and the Young's modulus, and shows a high effect of improving the ion exchange performance, among alkaline earth metal oxides. The content of MgO is preferably 0 to 6%. However, when the content of MgO becomes large, the density and the thermal expansion coefficient of the glass increase, and the glass tends to be devitrified. Therefore, it is preferred that the content thereof be 4% or less, 3% or less, 2% or less, or 1.5% or less.

CaO is a component which lowers the high temperature viscosity of a glass to enhance the meltability and the formability, or to enhance the strain point and the Young's modulus, and shows a high effect of improving the ion exchange performance, among alkaline earth metal oxides. The content of CaO is preferably 0 to 6%. However, when the content of CaO becomes large, the density and the thermal expansion coefficient of a glass increase, and the glass tends to be devitrified, and in addition, the ion exchange performance deteriorates in some cases. Therefore, it is preferred that the content thereof be 4% or less, or 3% or less.

SrO and BaO are components which lower the high temperature viscosity of a glass to enhance the meltability and the formability, or to enhance the strain point and the Young's modulus, and each content thereof is preferably 0 to 3%. When the content of SrO or BaO become large, the ion exchange performance tends to deteriorate. Further, the density and the thermal expansion coefficient of the glass increase, and the glass tends to be devitrified. It is preferred that the content of SrO be 2% or less, 1.5% or less, 1% or less, 0.5% or less, or 0.2% or less, and particularly 0.1% or less. It is preferred that the content of BaO be 2.5% or less, 2% or less, 1% or less, 0.8% or less, 0.5% or less, or 0.2% or less, and particularly 0.1% or less.

ZnO is a component which enhances the ion exchange performance of a glass, and in particular, shows a high effect of enhancing the compression stress value. Further, it is a component having an effect of lowering the high temperature viscosity without lowering the low temperature viscosity of the glass, and the content thereof can be set to 0 to 8%. However, when the content of ZnO becomes large, the glass manifests phase separation, the denitrification property deteriorates, and the density becomes large, thus, it is preferred that the content thereof be 6% or less, or 4% or less, 3% or less, 1% or less, 0.5% or less, and particularly 0.1% or less.

In the present invention, by limiting the total content of SrO+BaO to 0 to 5%, the ion exchange performance can be improved more effectively. That is, because SrO and BaO have an action of blocking the ion exchange reaction as described above, it is disadvantageous to contain a large amount of those components for obtaining a tempered glass having high mechanical strength. The preferable range of SrO+BaO is 0 to 3%, 0 to 2.5%, 0 to 2%, 0 to 1%, or 0 to 0.2%, and particularly 0 to 0.1%.

When the value obtained by dividing the total content of R′O by the total content of R₂O becomes large, a tendency of deteriorating the devitrification resistance of a glass appears. Therefore, it is preferred that the value in terms of mass fraction of R′ 0/R₂O be regulated to 0.5 or less, 0.4 or less, or 0.3 or less.

Because SnO₂ has an effect of improving the ion exchange performance, in particular, the compression stress value, it is preferred that the content of SnO₂ be 0.01 to 3%, 0.01 to 1.5%, or 0.1 to 1%. When the content of SnO₂ increases, there occurs a tendency that devitrification ascribable to SnO₂ is generated, and the glass is easily colored.

ZrO₂ has effects of remarkably improving the ion exchange performance and simultaneously, enhancing the Young's modulus and the strain point of a glass, and lowering the high temperature viscosity. Further, ZrO₂ has an effect of enhancing the viscosity around the liquidus viscosity of a glass, therefore, by inclusion of a given amount of ZrO₂, the ion exchange performance and the liquidus viscosity can be improved simultaneously. However, if the content thereof is too large, the devitrification resistance remarkably deteriorates in some cases. Thus, it is preferred that ZrO₂ be contained in an amount of 0.001 to 10%, 0.1 to 9%, 0.5 to 7%, 1 to 5%, or 2.5 to 5%.

B₂O₃ is a component having an effect of lowering the liquidus temperature, high temperature viscosity, and density of a glass and having an effect of improving the ion exchange performance of the glass, in particular, the compression stress value. Therefore, B₂O₃ can be contained together with the above-mentioned components. When the content of B₂O₃ is too large, there are possibilities that weathering occurs on the surface by ion exchange, the water resistance of the glass deteriorates, and the liquidus viscosity lowers. Further, the stress layer depth tends to lower. Therefore, the content of B₂O₃ is 0 to 6%, preferably 0 to 4%, and more preferably 0 to 3%.

TiO₂ is a component having an effect of improving the ion exchange performance. Further, it has an effect of lowering the high temperature viscosity of a glass. However, when the content thereof becomes too large, the glass is colored, the devitrification property deteriorates, and the density becomes high. Particularly in the case of using the glass as a cover glass of a display, if the content of TiO₂ becomes large, the transmittance of the glass tends to change when the melting atmosphere or raw materials are altered. Therefore, in a process of adhering a glass substrate to a device by utilizing light such as an ultraviolet cured resin, ultraviolet irradiation conditions tend to vary and stable production becomes difficult. Therefore, the content of TiO₂ is 4.5% or less, preferably 4% or less, 2% or less, 0.7% or less, 0.5% or less, 0.1% or less, or 0.01% or less.

In the present invention, it is preferred that ZrO₂ and TiO₂ be contained in the above-mentioned ranges from the standpoint of improving the ion exchange performance, and reagents may be used or impurities contained in raw materials may be used, as a TiO₂ source and a ZrO₂ source.

It is preferred that the content of Al₂O₃+ZrO₂ be defined as described below from the standpoint of simultaneous satisfaction of the denitrification resistance and high ion exchange performance.

When the content of Al₂O₃+ZrO₂ is preferably over 12% (more preferably 12.001% or more, 13% or more, 15% or more, 17% or more, 18% or more, or 19% or more), the ion exchange performance of a glass can be improved more effectively. When the content of Al₂O₃+ZrO₂ becomes too large, the denitrification property remarkably deteriorates, therefore, it is preferred that the content thereof be 28% or less (preferably, 25% or less, 23% or less, 22% or less, or 21% or less).

P₂O₅ is a component which enhances the ion exchange performance of a glass, and in particular, shows a high effect of increasing the depth of the compression stress layer, therefore, the content thereof can be set to 0 to 8%. However, when the content of P₂O₅ becomes large, the glass manifests phase separation, and the water resistance and the denitrification resistance tend to lower, thus, it is preferred that the content thereof be 5% or less, 4% or less, or 3% or less, and particularly 2% or less.

As the fining agent, one or more materials selected from the group consisting of As₂O₃, Sb₂O₃, CeO₂, F, SO₃, and Cl may be contained in an amount of 0.001 to 3%. It is necessary to refrain as much as possible from the use of As₂O₃ and Sb₂O₃, in terms of consideration to environments, and each content thereof is preferably limited to less than 0.1%, further less than 0.01%, and substantially no inclusion is desirable. CeO₂ is a component lowering the transmittance of a glass, and the content thereof is preferably limited to less than 0.1% and more preferably less than 0.01%. F may lower the low temperature viscosity of a glass, thereby inducing decrease in the compression stress value, thus, the content thereof is preferably limited to less than 0.1% and more preferably less than 0.01%. Therefore, SO₃ and Cl are preferable fining agents of the present invention, and one of or both of SO₃ and Cl be contained in an amount of preferably 0.001 to 3%, 0.001 to 1%, or 0.01 to 0.5%, and more preferably 0.05 to 0.4%.

Rare earth oxides such as Nb₂O₅, Y₂O₃ and La₂O₃ are components enhancing the Young's modulus of a glass. However, the cost of the raw material itself is high, and when the rare earth oxides are contained in a large amount, the denitrification resistance deteriorates. Therefore, it is desirable that the content thereof is limited to 3% or less, 2% or less, 1% or less, or 0.5% or less, and particularly to 0.1% or less.

Note that, in the present invention, transition metal elements causing intense coloration of a glass, such as Co and Ni, are not preferred, because they lower the transmittance of a glass substrate. In particular, in the case of using transition metal elements in a touch panel display, when the content thereof is large, the visibility of a touch panel display is deteriorated. Specifically, it is desirable that the use amount of raw materials or cullet be adjusted so that the content is 0.5% or less or 0.1% or less, and particularly 0.05% or less.

It is necessary to refrain as much as possible from the use of substances such as Pb and Bi in terms of consideration to environments, and the content thereof is preferably limited to less than 0.1%.

In the tempered glass substrate of the present invention, the suitable content range of each component can be appropriately selected to attain a preferable glass composition range. Specific examples thereof are shown below.

(1) A glass composition comprising, in terms of mass %, 40 to 70% of SiO₂, 12 to 21% of Al₂O₃, 0 to 2% of Li₂O, 10 to 19% of Na₂O, 0 to 15% of K₂O, 0 to 6% of MgO, 0 to 6% of CaO, 0 to 3% of SrO, 0 to 3% of BaO, 0 to 8% of ZnO, 0.01 to 3% of SnO₂, and 0 to 4.5% of TiO₂.

(2) A glass composition comprising, in terms of mass %, 40 to 70% of SiO₂, 12 to 21% of Al₂O₃, 0 to 2% of Li₂O, 10 to 19% of Na₂O, 0 to 15% of K₂O, 0 to 6% of MgO, 0 to 6% of CaO, 0 to 3% of SrO, 0 to 3% of BaO, 0 to 8% of ZnO, 0.01 to 3% of SnO₂, 0.001 to 10% of ZrO₂, and 0 to 4.5% of TiO₂.

(3) A glass composition comprising, in terms of mass %, 40 to 70% of SiO₂, 12 to 21% of Al₂O₃, 0 to 1% of Li₂O, 10 to 19% of Na₂O, 0 to 10% of K₂O, 0 to 6% of MgO, 0 to 6% of CaO, 0 to 3% of SrO, 0 to 3% of BaO, 0 to 8% of ZnO, 0.01 to 3% of SnO₂, and 0 to 4.5% of TiO₂.

(4) A glass composition comprising, in terms of mass %, 40 to 70% of SiO₂, 12 to 21% of Al₂O₃, 0 to 1% of Li₂O, 10 to 19% of Na₂O, 0 to 10% of K₂O, 0 to 6% of MgO, 0 to 6% of CaO, 0 to 3% of SrO, 0 to 3% of BaO, 0 to 8% of ZnO, 0.01 to 3% of SnO₂, 0.001 to 10% of ZrO₂, and 0 to 4.5% of TiO₂.

(5) A glass composition comprising, in terms of mass %, 40 to 70% of SiO₂, 12 to 19% of Al₂O₃, 0 to 6% of B₂O₃, 0 to 2% of Li₂O, 10 to 19% of Na₂O, 0 to 15% of K₂O, 0 to 6% of MgO, 0 to 6% of CaO, 0 to 3% of SrO, 0 to 3% of BaO, 0 to 6% of ZnO, 0.001 to 10% of ZrO₂, 0.1 to 1% of SnO₂, and 0 to 4.5% of TiO₂, which does not substantially include As₂O₃ and Sb₂O₃.

(6) A glass composition comprising, in terms of mass %, 40 to 70% of SiO₂, 12 to 18% of Al₂O₃, 0 to 4% of B₂O₃, 0 to 2% of Li₂O, 11 to 17% of Na₂O, 0 to 6% of K₂O, 0 to 6% of MgO, 0 to 6% of CaO, 0 to 3% of SrO, 0 to 3% of BaO, 0 to 6% of ZnO, 0.1 to 1% of SnO₂, 0.001 to 10% of ZrO₂, and 0 to 4.5% of TiO₂, which does not substantially include As₂O₃ and Sb₂O₃.

(7) A glass composition comprising, in terms of mass %, 40 to 63% of SiO₂, 12 to 17.5% of Al₂O₃, 0 to 3% of B₂O₃, 0 to 0.1% of Li₂O, 10 to 17% of Na₂O, 0 to 7% of K₂O, 0 to 5% of MgO, 0 to 4% of CaO, 0 to 3% of SrO+BaO, and 0.01 to 2% of SnO₂, and 0 to 4.5% of TiO₂, which does not substantially include As₂O₃ and Sb₂O₃, and in which the value of (Na₂O+K₂O)/Al₂O₃ is 0.9 to 1.6 and K₂O/Na₂O is 0 to 0.4, in terms of mass fraction.

(8) A glass composition comprising, in terms of mass %, 40 to 70% of SiO₂, 12 to 21% of Al₂O₃, 0 to 2% of Li₂O, 10 to 20% of Na₂O, 0 to 9% of K₂O, 0 to 5% of MgO, 0 to 0.5% of TiO₂, and 0.01 to 3% of SnO₂.

(9) A glass composition comprising, in terms of mass %, 40 to 70% of SiO₂, 12 to 21% of Al₂O₃, 0 to 2% of Li₂O, 10 to 20% of Na₂O, 0 to 9% of K₂O, 0 to 5% of MgO, 0 to 0.5% of TiO₂, and 0.01 to 3% of SnO₂, and not substantially including As₂O₃ and Sb₂O₃.

(10) A glass composition comprising, in terms of mass %, 40 to 65% of SiO₂, 12 to 21% of Al₂O₃, 0 to 1% of Li₂O, 10 to 20% of Na₂O, 0 to 9% of K₂O, 0 to 5% of MgO, 0 to 0.5% of TiO₂, and 0.01 to 3% of SnO₂, having the value of (Na₂O+K₂O)/Al₂O₃ of 0.7 to 2 in terms of mass fraction, and not substantially including As₂O₃, Sb₂O₃, and F.

(11) A glass composition characterized by including, in terms of mass %, 40 to 65% of SiO₂, 12 to 21% of Al₂O₃, 0 to 1% of Li₂O, 10 to 20% of Na₂O, 0 to 9% of K₂O, 0 to 5% of MgO, 0 to 0.5% of TiO₂, 0.01 to 3% of SnO₂, and 0 to 8% of MgO+CaO+SrO+BaO, having the value of (Na₂O+K₂O)/Al₂O₃ of 0.9 to 1.7 in terms of mass fraction, and not substantially including As₂O₃, Sb₂O₃, and F.

(12) A glass composition characterized by including, in terms of mass %, 40 to 63% of SiO₂, 12 to 19% of Al₂O₃, 0 to 3% of B₂O₃, 0 to 1% of Li₂O, 10 to 20% of Na₂O, 0 to 9% of K₂O, 0 to 5% of MgO, 0 to 0.1% of TiO₂, 0.01 to 3% of SnO₂, 0.001 to 10% of ZrO₂, and 0 to 8% of MgO+CaO+SrO+BaO, having the value of (Na₂O+K₂O)/Al₂O₃ of 1.2 to 1.6 in terms of mass fraction, and not substantially including As₂O₃, Sb₂O₃, and F.

(13) A glass composition characterized by including, in terms of mass %, 40 to 63% of SiO₂, 12 to 17.5% of Al₂O₃, 0 to 3% of B₂O₃, 0 to 1% of Li₂O, 10 to 20% of Na₂O, 0 to 9% of K₂O, 0 to 5% of MgO, 0 to 0.1% of TiO₂, 0.01 to 3% of SnO₂, 0.1 to 8% of ZrO₂, and 0 to 8% of MgO+CaO+SrO+BaO, having the value of (Na₂O+K₂O)/Al₂O₃ of 1.2 to 1.6 in terms of mass fraction, and not substantially including As₂O₃, Sb₂O₃, and F.

(14) A glass composition characterized by including, in terms of mass %, 40 to 59% of SiO₂, 12 to 15% of Al₂O₃, 0 to 3% of B₂O₃, 0 to 0.1% of Li₂O, 10 to 20% of Na₂O, 0 to 7% of K₂O, 0 to 5% of MgO, 0 to 0.1% of TiO₂, 0.01 to 3% of SnO₂, 1 to 8% of ZrO₂, and 0 to 8% of MgO+CaO+SrO+BaO, having the value of (Na₂O+K₂O)/Al₂O₃ of 1.2 to 1.6 in terms of mass fraction, and not substantially including As₂O₃, Sb₂O₃, and F.

The tempered glass substrate of the present invention has the above-mentioned glass composition and has a compression stress layer on the surface of the glass substrate. The compression stress of the compression stress layer on the surface is preferably 300 MPa or more, more preferably 600 MPa or more, 800 MPa or more, 1000 MPa or more, still more preferably 1200 MPa or more, and still further preferably 1300 MPa or more. The larger the compression stress is, the greater the mechanical strength of a glass substrate is. On the other hand, when extremely large compression stress is formed on the surface of the glass substrate, there is a possibility that micro cracks are generated on the substrate surface, which may lead to decrease in the strength of the glass. Because there is a possibility that the tensile stress present in the glass substrate becomes extremely high, the compression stress is preferably set to be 2500 MPa or less. In order to increase the compression stress, it may be advantageous to increase the content of Al₂O₃, TiO₂, ZrO₂, MgO, ZnO, or SnO₂, or to decrease the content of SrO or BaO. Alternatively, it may be advantageous to shorten the time necessary for ion exchange, or to decrease the temperature of an ion exchange solution.

It is preferred that the depth of a compression stress layer on the surface be 10 μm or more, 15 μm or more, 20 μm or more, or 30 μm or more. The larger the thickness of a compression stress layer on the surface is, the more difficult it is that the glass substrate is cracked even if the glass substrate has a deep flaw. On the other hand, it may become difficult to cut the glass substrate, and the internal tensile stress may increase extremely to cause breakage, it is preferred that the thickness of the compression stress layer on the surface be 500 μm or less, 100 μm or less, 80 μm or less, or 60 μm or less. In order to increase the thickness of the compression stress layer, it may be advantageous to increase the content of K₂O, P₂O₅, TiO₂, or ZrO₂, or to decrease the content of SrO or BaO. Further, it may be advantageous to elongate the time necessary for ion exchange, or to raise the temperature of an ion exchange solution.

The tensile stress in a glass substrate is 150 MPa or less, preferably 100 MPa or less, and more preferably 50 MPa or less. The smaller the value is, the less likely it is that the breakage of glass occurs due to a defect in a glass substrate. However, when the value becomes extremely small, the compression stress value on the surface of the glass substrate decreases and the stress depth decreases, thus, it is preferred that the value be 1 MPa or more, 10 MPa or more, or 15 MPa or more.

The tempered glass substrate of the present invention have a plate thickness of 1.5 mm or less, preferably 0.7 mm or less, or 0.5 mm or less, and particularly 0.3 mm or less. When the plate thickness of the glass substrate is smaller, the weight of the glass substrate can be reduced more. The tempered glass substrate of the present invention has a merit that even if the plate thickness is decreased, the glass substrate is not broken easily. It is advantage to perform forming of a glass by an overflow down draw method, because the thickness reduction and smoothening of the glass can be attained without polishing.

The tempered glass substrate of the present invention preferably has an unpolished surface, and the average surface roughness (Ra) of the unpolished surface is preferably 10 Å or less, more preferably 5 Å or less, 4 Å or less, still more preferably 3 Å or less, and most preferably 2 Å or less. Note that the average surface roughness (Ra) of the surface may be measured by a method according to SEMI D7-97 “Measurement method of surface roughness of FPD glass substrate”. The theoretical strength of glass is essentially very high, but breakage often occurs even with a stress which is by far lower than the theoretical strength. This phenomenon occurs because a small defect called Griffith flaw is generated on the surface of a glass substrate after forming of the glass, for example, in a polishing process. Therefore, when the surface of the tempered glass substrate is not polished, the original mechanical strength of the glass substrate is lowered, and the glass substrate is not broken easily. Further, when the surface of the glass substrate is not polished, a polishing process can be omitted in the glass substrate production process, thus, the production cost of the glass substrate can be decreased. In the tempered glass substrate of the present invention, if the both surfaces of a glass substrate are not polished, the glass substrate becomes more difficult to break. In the tempered glass substrate of the present invention, a chamfering process, etching treatment, and the like may be performed on a cut surface of the glass substrate to prevent breakage occurring from the cut surface of a glass substrate. In order to obtain the unpolished surface, it may be advantageous to carry out forming of the glass by an overflow down draw method.

In the tempered glass substrate of the present invention, the liquidus temperature of the glass is preferably 1200° C. or lower, 1050° C. or lower, 1030° C. or lower, 1010° C. or lower, 1000° C. or lower, 950° C. or lower, or 900° C. or lower, and particularly preferably 870° C. or lower. In order to decrease the liquidus temperature, it may be advantageous to increase the content of Na₂O, K₂O, or B₂O₃, or to decrease the content of Al₂O₃, Li₂O, MgO, ZnO, TiO₂, or ZrO₂.

In the tempered glass substrate of the present invention, the liquidus viscosity of the glass is preferably 10^(4.0) dPa·s or more, 10^(4.3) dPa·s or more, 10^(4.5) dPa·s or more, 10^(5.0) dPa·s or more, 10^(5.4) dPa·s or more, 10^(5.8) dPa·s or more, 10^(6.0) dPa·s or more, or 10^(6.2) dPa·s or more. In order to improve liquidus viscosity, it may be advantageous to increase the content of Na₂O or K₂O, or to decrease the content of Al₂O₃, Li₂O, MgO, ZnO, TiO₂, or ZrO₂.

Note that when the liquidus viscosity is higher and the liquidus temperature is lower, the denitrification resistance of the glass is more excellent and the formability of a glass substrate is more excellent. When the liquidus temperature of a glass is 1200° C. or lower and the liquidus viscosity of the glass is 10^(4.0) dPa·s or more, forming is possible by an overflow down draw method.

The tempered glass substrate of the present invention has a glass density of preferably 2.8 g/cm³ or less, more preferably 2.7 g/cm³ or less, and still more preferably 2.6 g/cm³ or less. When the glass density is smaller, the weight of the glass substrate can be reduced more. Here, “density” denotes a value measured by a known Archimedes method. In order to lower the glass density, it may be advantageous to increase the content of SiO₂, P₂O₅, or B₂O₃, or to decrease the content of alkali metal oxides, alkaline earth metal oxides, ZnO, ZrO₂, or TiO₂.

The tempered glass substrate of the present invention has a glass thermal expansion coefficient in the temperature range of 30 to 380° C. of preferably 70 to 110×10⁻⁷/° C., more preferably 75 to 110×10⁻⁷/° C., still more preferably 80 to 110×10⁻⁷/° C., and particularly preferably 85 to 110×10⁻⁷/° C. When the thermal expansion coefficient of a glass is set within the above-mentioned range, the thermal expansion coefficient thereof tends to match those of members such as metals and organic adhesives, and peeling of members such as metals and organic adhesives can be prevented. Here, “thermal expansion coefficient” denotes a value measured in the temperature range of 30 to 380° C. using a dilatometer. In order to increase the thermal expansion coefficient, it may be advantageous to increase the content of alkali metal oxides or alkaline earth metal oxides, and, conversely, in order to decrease the thermal expansion coefficient, it may be advantageous to decrease the content of alkali metal oxides or alkaline earth metal oxides.

The tempered glass substrate of the present invention has a strain point of preferably 500° C. or higher, more preferably 510° C. or higher, 520° C. or higher, 540° C. or higher, or 550° C. or higher, and most preferably 560° C. or higher. When the strain point of a glass is higher, the heat resistance of the glass is more excellent, and even if a thermal treatment is performed on the tempered glass substrate, the tempered layer does not disappear easily. When the strain point of the glass is high, stress relaxation does not occur easily during ion exchange, thus, a high compression stress value can be obtained. In order to increase the strain point of a glass, it may be advantages to decrease the content of alkali metal oxides, or to increase the content of alkaline earth metal oxides, Al₂O₃, ZrO₂, or P₂O₅.

It is preferred that the tempered glass substrate of the present invention have a temperature corresponding to a glass high temperature viscosity of 10^(2.5) dPa·s of 1650° C. or lower, 1500° C. or lower, 1450° C. or lower, 1430° C. or lower, 1420° C. or lower, or 1400° C. or lower. The temperature corresponding to the glass high temperature viscosity of 10^(2.5) dPa·s corresponds to the glass melting temperature, and when the temperature corresponding to a glass high temperature viscosity of 10^(2.5) dPa·s is lower, the glass can be melted at lower temperature. Therefore, when the temperature corresponding to a glass high temperature viscosity of 10^(2.5) dPa·s is lower, burden on a glass production facility such as a melting furnace becomes smaller and the bubble quality of the glass substrate can be improved. Therefore, when the temperature corresponding to the glass high temperature viscosity of 10^(2.5) dPa·s is lower, the glass substrate can be produced at lower cost. In order to lower the temperature corresponding 10^(2.5) dPa·s, it may be advantages to increase the content of alkali metal oxides, alkaline earth metal oxides, ZnO, B₂O₃, or TiO₂, or to decrease the content of SiO₂ or Al₂O₃.

The tempered glass substrate of the present invention preferably has a Young's modulus of 70 GPa or more, more preferably 73 GPa or more, and still more preferably 75 GPa or more. Therefore, in the case of using the tempered glass substrate as a cover glass of a display, when the Young's modulus is higher, the deformation amount when the surface of the cover glass is pushed by a pen or finger becomes smaller, and hence leading to reduction of damage caused to an internal display.

Further, the glass of the present invention comprises, in terms of mass %, 40 to 71% of SiO₂, 10 to 21% of Al₂O₃, 0 to 3.5% of Li₂O, 10 to 20% of Na₂O, and 0 to 15% of K₂O, preferably comprises, in terms of mass %, 40 to 71% of SiO₂, 10 to 21% of Al₂O₃, 0 to 2% of Li₂O, 10 to 19% of Na₂O, 0 to 15% of K₂O, 0 to 6% of MgO, 0 to 6% of CaO, 0 to 3% of SrO, 0 to 3% of BaO, 0 to 8% of ZnO, and 0.01 to 3% of SnO₂, and more preferably comprises, in terms of mass %, 40 to 71% of SiO₂, 10 to 21% of Al₂O₃, 0 to 1% of Li₂O, 10 to 19% of Na₂O, 0 to 10% of K₂O, 0 to 6% of MgO, 0 to 6% of CaO, 0 to 3% of SrO, 0 to 3% of BaO, 0 to 8% of ZnO, 0.01 to 3% of SnO₂, and 0.001 to 10% of ZrO₂. The reason for limiting the glass composition to the above-mentioned range and the preferable range thereof in the glass of the present invention are the same as those for the tempered glass substrate described above, therefore, descriptions thereof are omitted here. Further, naturally, the glass of the present invention can have simultaneously the properties and effects of the tempered glass substrate described above.

In the glass of the present invention, because the constituent components are limited in the above-mentioned ranges, the ion exchange performance is excellent, and it is easy to set the surface compression stress to 600 MPa or more and set the depth of the compression stress layer to 10 μm or more.

The glass according to the present invention can be produced by placing a glass raw material which is prepared to have a glass composition within the above-mentioned composition range in a continuous melting furnace, melting the glass raw material by heating at 1500 to 1600° C., fining the resultant, feeding the resultant to a forming apparatus, and forming the molten glass into a plate shape having a plate thickness of 1.5 mm or less, and gradually annealing the plate.

For forming the glass into a plate shape, it is preferable to adopt an overflow down draw method. When the glass substrate is formed by the overflow down draw method, a glass substrate which is not polished and has an excellent surface quality can be produced. The reason for this is as follows: in the case of adopting the overflow down draw method, the surfaces to be the surfaces of the glass substrate do not come in direct contact with a trough-shaped refractory, and is formed in the form of free surface, and hence, a glass substrate which is not polished and has excellent surface quality can be formed. Here, the overflow down draw method is a method in which a glass in molten condition is allowed to overflow from both sides of a heat-resistant trough-shaped structure, and the overflown molten glasses are draw-formed downwardly while combining them at the lower end of the trough-shaped structure, to thereby produce a glass substrate. The structure and material of the trough-shaped structure are not particularly limited as long as they provide desired size and surface precision of the glass substrate and can realize quality usable in the glass substrate. Further, any method may be used to apply force to the glass substrate to perform downward draw forming. For example, there may be adopted a method involving rotating a heat resistant roll having sufficiently large width in the state of being in contact with a glass substrate, to thereby draw the glass substrate, and a method involving allowing several pairs of heat resistant rolls to come into contact with only end surfaces of the glass substrate to thereby draw the glass substrate. The glass of the present invention is excellent in denitrification resistance and has a viscosity property suitable for forming, thus, forming by the overflow down draw method can be carried out with good precision by using the glass of the present invention. When the liquidus temperature is 1200° C. or lower and the liquidus viscosity is 10^(4.0) dPa·s or more, the glass substrate can be produced by an overflow down draw method.

Note that, in the present invention, a method other than the overflow down draw method can be adopted when high surface quality is not required. For example, various forming methods can be adopted, such as down draw methods (a slot down method and a re-draw method), a float method, a roll out method, and a press method. For example, if a glass is formed by a press method, a small-sized glass substrate can be produced with good efficiency.

For producing the tempered glass substrate of the present invention, first, the above-mentioned glass is prepared. Next, a tempering treatment is performed. The glass substrate may be cut into a given size before the tempering treatment, however, it is preferable to perform the cutting after the tempering treatment, because the production cost can be reduced. It is desirable that the tempering treatment is performed by an ion exchange treatment. The ion exchange treatment can be performed, for example, by immersing a glass plate in a potassium nitrate solution at 400 to 550° C. for 1 to 8 hours. Optimum ion exchange conditions may be selected in view of glass viscosity property, application, plate thickness, tensile stress in glass, and the like.

EXAMPLES

The present invention is described based on examples below.

Tables 1 to 4 show glass compositions and properties of examples of the present invention (sample Nos. 1 to 26). Note that, in the tables, expression “none” means “not measured”. In addition, sample Nos. 14, 24 and 25 are reference examples.

TABLE 1 No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 SiO₂ 51.9 52.9 54.4 52.9 60.9 62.4 60.4 54.4 Al₂O₃ 19.0 19.0 16.0 16.0 16.0 13.0 13.0 13.0 Na₂O 16.0 16.0 16.0 16.0 16.0 16.0 16.0 16.0 Li₂O — — — — — — — — K₂O 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 ZrO₂ 5.0 2.5 5.0 2.5 — 2.5 — 5.0 TiO₂ — 2.5 2.5 4.5 — — 2.5 4.5 B₂O₃ 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 MgO 2.0 1.0 — 2.0 1.0 — 2.0 1.0 CaO 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 SnO₂ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Density (g/cm³) 2.56 2.53 2.57 2.56 2.47 2.50 2.49 2.59 Ps (° C.) 575 558 562 550 520 523 519 552 Ta (° C.) 622 600 604 588 561 564 557 591 Ts (° C.) 841 806 805 775 761 762 741 775.5 10⁴ (° C.) 1171 1152 1153 1088 1138 1135 1083 1091 10³ (° C.) 1335 1334 1333 1259 1349 1340 1277 1260 10^(2.5) (° C.) 1444 1452 1451 1375 1484 1472 1406 1372 Young's modulus none None none none none none none none (GPa) α (×10⁻⁷/° C.) 94 96 94 96 95 92 96 96 TL (° C.) none 1005 <900 930 <900 <900 <900 <900 logη TL none 5.1 >6.2 5.4 >5.8 >5.8 >5.5 >5.8 Compression stress 1462 1366 1338 1348 909 842 943 1322 value (MPa) Stress layer depth 18 20 17 16 23 23 18 15 (μm) Internal tensile 28 28 24 22 22 20 18 21 stress (MPa)

TABLE 2 No. 9 No. 10 No. 11 No. 12 No. 13 No. 14 No. 15 SiO₂ 52.4 50.4 53.9 53.9 61.4 59.4 56.9 Al₂O₃ 16.0 16.0 16.0 14.5 13.0 13.0 13.0 Na₂O 16.0 16.0 16.0 16.0 11.0 7.0 15.0 Li₂O — — — — — — — K₂O 2.0 2.0 2.0 2.0 6.0 10.5 5.0 ZrO₂ 5.0 5.0 5.0 6.5 2.5 4.0 4.0 TiO₂ 2.5 4.5 — — — — — B₂O₃ 2.0 2.0 2.0 2.0 2.0 2.0 2.0 MgO 2.0 2.0 2.0 2.0 2.0 2.0 2.0 CaO 2.0 2.0 3.0 3.0 2.0 2.0 2.0 SnO₂ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Density (g/cm³) 2.57 2.59 2.55 2.57 2.47 2.49 2.53 Ps (° C.) 563 563 557 562 544 574 529 Ta (° C.) 605 603 601 606 589 623 570 Ts (° C.) 805 792 808 812 812 867 773 10⁴ (° C.) 1123 1097 1137 1130 1205 1253 1122 10³ (° C.) 1289 1258 1303 1291 1406 1447 1300 10^(2.5) (° C.) 1397 1363 1410 1397 1534 1570 1417 Young's modulus none none none none none none none (GPa) α (×10⁻⁷/° C.) 95 95 95 94 90 88 100 TL (° C.) none none none none 945 1075 855 logη TL none none none none 6.0 5.3 6.4 Compression stress 1293 1407 1226 1274 858 623 1020 value (MPa) Stress layer depth 23 21 23 14 25 36 24 (μm) Internal tensile 32 30 29 18 23 24 26 stress (MPa)

TABLE 3 No. 16 No. 17 No. 18 No. 19 No. 20 No. 21 No. 22 No. 23 SiO₂ 55.9 55.9 55.9 57.9 55.9 55.9 55.9 58.4 Al₂O₃ 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 Na₂O 15.0 12.5 11.5 12.0 15.0 16.0 15.0 13.0 Li₂O — — — — — — — — K₂O 5.0 4.0 5.0 4.0 5.0 4.0 3.5 3.5 ZrO₂ 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 TiO₂ — — — — — — 1.5 3.0 B₂O₃ 2.0 2.5 2.5 — 2.0 2.0 2.0 — MgO 2.0 4.0 3.0 4.0 3.0 3.0 3.0 3.0 CaO 2.0 3.0 4.0 4.0 1.0 1.0 1.0 1.0 SnO₂ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Cl (ppm) 50 50 — 100 100 150 100 150 SO₃ (ppm) — 10 20 — — — 10 — Density (g/cm³) 2.55 2.56 2.56 2.57 2.55 2.55 2.55 2.55 Ps (° C.) 533 558 558 589 538 536 551 591 Ta (° C.) 574 602 601 634 580 578 593 637 Ts (° C.) 780 809 811 847 791 785 800 855 10⁴ (° C.) 1130 1141 1145 1168 1142 1133 1139 1195 10³ (° C.) 1305 1308 1314 1335 1317 1307 1312 1372 10^(2.5) (° C.) 1418 1417 1424 1443 1430 1420 1424 1486 Young's modulus none none none none none none none none (GPa) α (×10⁻⁷/° C.) 100 89 90 89 99 100 95 88 TL (° C.) 875 none none none 895 895 905 none logη TL 6.3 none none none 6.2 6.1 6.1 none Compression stress 949 1087 993 1079 1048 1052 1186 1245 value (MPa) Stress layer depth 35 20 23 23 37 35 30 32 (μm) Internal tensile 36 23 24 26 42 40 38 43 stress (MPa)

TABLE 4 No. 24 No. 25 No. 26 SiO₂ 69.9 70.6 57.3 Al₂O₃ 13.4 13.5 13.0 Na₂O 8.2 8.3 14.5 Li₂O 1.9 1.9 — K₂O 5.4 5.4 4.9 ZrO₂ — — 4.0 TiO₂ — — — B₂O₃ — — 2.0 MgO — — 2.0 CaO — — 2.0 SnO₂ 1.2 0.3 0.3 Density (g/cm³) 2.41 2.39 2.54 Ps (° C.) 473 467 523 Ta (° C.) 521 514 563 Ts (° C.) 765 756 762 10⁴ (° C.) 1210 1205 1100 10³ (° C.) 1453 1454 1280 10^(2.5) (° C.) 1609 1612 1396 Young's modulus (GPa) 74 73 75 α (×10⁻⁷/° C.) 83 84 100 TL (° C.) 900 910 855 logη TL 6.1 5.9 6.2 Compression stress 550 500 1,020 value (MPa) Stress layer depth (μm) 28 29 25 Internal tensile stress 16 15 27 (MPa)

Each of the samples in Tables 1 to 4 were produced as described below. First, a glass raw material was prepared so as to have a glass composition shown in the table, and the raw material was melted at 1580° C. for 8 hours using a platinum pot. Thereafter, the molten glass was cast on a carbon plate and formed into a plate shape. Various properties were evaluated for the resultant glass plate.

The density was measured by a known Archimedes method.

The strain point Ps and the slow annealing point Ta were measured based on a method of ASTM C336.

The softening point Ts was measured based on a method of ASTM C338.

Temperatures corresponding to glass viscosities 10^(4.0) dPa·s, 10^(3.0) dPa·s, and 10^(2.5) dPa·s were measured by a platinum sphere lifting method.

The Young's modulus was measured by a bending resonance method.

As the thermal expansion coefficient α, an average thermal expansion coefficient in the temperature range of 30 to 380° C. was measured using a dilatometer.

As for the liquidus temperature TL: a glass was ground, and a glass powder which passes through a standard sieve of 30 mesh (mesh opening 500 μm) and remaining on 50 mesh (mesh opening 300 μm) was placed in a platinum boat, kept in a temperature gradient furnace for 24 hours, then, the crystal thereof deposited, and the temperature at this stage was referred to as liquidus temperature.

The liquidus viscosity log η TL shows the viscosity of each glass at the liquidus temperature.

As a result, the obtained glass substrate had a density of 2.59 g/cm³ or less, a thermal expansion coefficient of 83 to 100×10⁻⁷/° C., thus, the glass substrate was suitable as a tempered glass substrate. The liquidus viscosity was as high as 10^(5.1) dPa·s or more and overflow down draw forming is possible, further, the temperature at 10^(2.5) dPa·s was as low as 1612° C. or lower, thus, it is supposed that a large amount of glass substrates can be fed at low cost with high productivity. Note that the untempered glass substrate and tempered glass substrate are not substantially different in glass composition as the whole glass substrate, even though the glass compositions thereof are microscopically different on the surface of the glass substrate. Therefore, for property values such as density and viscosity, the untempered glass substrate and tempered glass substrate are not substantially different. Subsequently, both surfaces of each of the glass substrates of sample Nos. 1 to 26 were subjected to optical polishing, then, an ion exchange treatment was performed. Sample Nos. 1 to 8, 13 to 15, 24, and 25 were immersed in a KNO₃ melted salt at 430° C. for 4 hours, and sample Nos. 9 to 12, 16 to 23, and 26 were immersed in a KNO₃ melted salt at 460° C. for 4 hours. After completion of the treatment, the surface of each sample was washed, then, compression stress value and stress layer depth (depth of compression stress layer) were calculated from the number of interference stripes and clearance thereof observed using a surface stress meter (FSM-6000 manufactured by Toshiba Corporation). In calculation, the refractive index of a sample was 1.53, and the photoelastic constant was 28 [(nm/cm)/MPa].

As a result, in the glass substrates of sample Nos. 1 to 26 which are examples of the present invention, compression stress of 500 MPa or more was generated on its surface, and its depth was as deep as 14 μm or more. The internal tensile stress in the substrate having a plate thickness of 1 mm was as low as 43 MPa or less.

Glass test pieces having different internal stresses were produced by using the glass sample of sample No. 15, which is an example of the present invention, and by changing the thickness of the glass substrate and the ion exchange conditions, to thereby evaluate the condition of breakage by internal stress.

The evaluation method is as described below.

From the glass of sample No. 15, a glass plate having a plate thickness of 0.5 mm and a glass plate having a plate thickness of 0.7 mm were produced, and were each cut into a size of 35 mm×35 mm. On each of the thus obtained glass substrates, ion exchange was carried out under conditions of 460° C. for 6 hours, 460° C. for 8 hours, and 490° C. for 6 hours, then, compression stress was measured. The results thereof are shown in Table 5. Note that the compression stress was measured by the same method as described above, and the internal stress (internal tensile stress in glass substrate) was calculated according to the above-mentioned formula from the compression stress value.

TABLE 5 Depth of Compression compression Internal stress (MPa) Ion exchange stress value stress layer 0.7 mm 0.5 mm condition (MPa) (μm) thick thick 460° C. for 6 hours 540 55 50 76 460° C. for 6 hours 537 58 53 81 490° C. for 6 hours 429 76 59 94

For the glass substrates in Table 5, to check whether the glass substrate is broken or not when a flaw is formed on its surface and the flaw reaches to the internal stress layer, the following procedure was conducted: a scribe machine in which a wheel tip material is diamond was used, the air pressure was set to 0.3 MPa, the wheel tip blade angle was set to 125°, the wheel tip polishing grade was set to D521, and a wheel tip was allowed to hit the surface of the glass substrate to break the glass substrate.

Table 6 shows the number of broken pieces after breakage of the glass substrate. For reference, the number of broken pieces of the glass substrate which did not undergo ion exchange and has an internal stress of 0 is also shown. As is apparent from Table 6, it is understood that when the internal stress is 50 to 94 MPa, the number of broken pieces is about the same as that of the glass substrate having an internal stress of 0.

TABLE 6 Internal stress Number of broken pieces 0 2 50 2 53 2 59 3 64 3 76 3 81 3 94 3

Note that, in the above-mentioned examples, a glass was melted, formed by casting, and then optically polished before the ion exchange treatment, for convenience of explanation of the present invention. In the case of production in industrial scale, it is preferred that a glass substrate be manufactured by an overflow down draw method and the like, and an ion exchange treatment be carried out in the state that the both surfaces of the glass substrate are unpolished.

INDUSTRIAL APPLICABILITY

The tempered glass substrate of the present invention is suitable as a cover glass or a touch panel display substrate for cellular phones, digital cameras, PDA, and solar batteries. The tempered glass substrate of the present invention is expected to be applied to applications requiring high mechanical strength, for example, window glasses, magnetic disk substrates, flat panel display substrates, solid-state imaging device cover glasses, and tableware, in addition to the above-mentioned applications. 

The invention claimed is:
 1. A tempered glass substrate, which has a compression stress layer on a surface thereof, and has a glass composition comprising, in terms of mass %, 40 to 70% of SiO₂, 12 to 23% of Al₂O₃, 0 to 3.5% of Li₂O, 10 to 20% of Na₂O, 2% or less of K₂O, and 0 to 4.5% of TiO₂, wherein a mass ratio of K₂O/Na₂O is 0 to 0.2 and a mass ratio of (MgO+CaO+SrO+BaO)/(Li₂O+Na₂O+K₂O) is 0.5 or less, wherein the tempered glass substrate has a plate thickness of 1.5 mm or less, and wherein the surface is an unpolished surface formed by an overflow down draw method and an internal tensile stress in the tempered glass substrate is 15 to 150 MPa.
 2. The tempered glass substrate according to claim 1, wherein the plate thickness is 0.7 mm or less.
 3. The tempered glass substrate according to claim 1, which is chemically tempered.
 4. The tempered glass substrate according to claim 1, wherein a compression stress of the surface is 300 MPa or more.
 5. The tempered glass substrate according to claim 1, wherein a depth of the compression stress layer is 10 μm or more.
 6. The tempered glass substrate according to claim 1, wherein the content of TiO₂ is 4% or less.
 7. The tempered glass substrate according to claim 1, wherein the internal tensile stress is 15 to 100 MPa.
 8. The tempered glass substrate according to claim 1, which is used for a cover glass of a display.
 9. The tempered glass substrate according to claim 1, which is used for a cover glass of a solar battery.
 10. The tempered glass substrate according to claim 1, wherein the glass composition further comprises, in terms of mass %, less than 0.1% of F.
 11. The tempered glass substrate according to claim 1, wherein the tempered glass substrate is cut after tempering.
 12. The tempered glass substrate according to claim 1, wherein the glass composition comprises 0 to 0.1% of Li₂O.
 13. The tempered glass substrate according to claim 1, wherein the glass composition further comprises, in terms of mass %, less than 0.1% of As₂O₃, less than 0.1% of Sb₂O₃, and 0.01 to 3% of SnO₂.
 14. The tempered glass substrate according to claim 1, wherein the unpolished surface has an average surface roughness Ra of 10 Å or less.
 15. The tempered glass substrate according to claim 1, wherein the glass composition further comprises, in terms of mass %, 0.001 to 10% of ZrO₂.
 16. The tempered glass substrate according to claim 1, wherein the tempered glass substrate is formed into a plate shape by a down draw method.
 17. The tempered glass substrate according to claim 1, wherein the tempered glass substrate is formed into a plate shape by an overflow down draw method.
 18. A method of producing a tempered glass substrate, comprising the steps of: melting a glass raw material which is prepared to have a glass composition comprising, in terms of mass %, 40 to 70% of SiO₂, 12 to 23% of Al₂O₃, 0 to 3.5% of Li₂O, 10 to 20% of Na₂O, 2% or less of K₂O, and 0 to 4.5% of TiO₂, wherein a mass ratio of K₂O/Na₂O is 0 to 0.2 and a mass ratio of (MgO+CaO+SrO+BaO)/(Li₂O+Na₂O+K₂O) is 0.5 or less; forming the resultant into a plate shape by an overflow down draw method to obtain a plate thickness of 1.5 mm or less and an unpolished surface; and performing an ion exchange treatment to form a compression stress layer on the unpolished surface of the tempered glass substrate and an internal tensile stress of 15 to 150 MPa in the tempered glass substrate. 